Dyeing keratinous fibers with n-alkyl-n-carbamylalkyl-isopicramic acid compounds

ABSTRACT

This disclosure is concerned with dyeing compositions containing certain N-alkyl-N-carbamylalkyl-isopicramic acid compounds and to methods of dyeing keratinous fibers with these compositions.

United States Patent [72] Inventor Jerzy Josef Bartoszewicz Twickenham[21] Appl. No. 751,632

[22] Filed May 23, 1968 [23] Division of Ser. No. 413,986, Nov. 25,1964, Pat. No. 3,420,883

[45] Patented Nov. 2, 1971 [73] Assignee Lever Brothers Company NewYork, N.Y.

[32] Priority Nov. 26, 1963 [33] Great Britain [54] DYEING KERATINOUSFIBERS WITH N-ALKYL- N-CARBAMYLALKYL-ISOPICRAMIC ACID COMPOUNDS I 6Claims, No Drawings [52] US. Cl 8/l0.l, 8/10, 260/247.2 A, 260/2475 R,260/559 A [51] Int. Cl A6lk 7/12 [50] Field of Search 260/559 A, 247.5R, 247.2 A; 8/101, 10

[56] References Cited OTHER REFERENCES Chemical Abstracts, Vol. 53, p.18405g (1959).

Primary Examiner-Albert T. Meyers Assistant Examiner- Vera C. ClarkeAttorney-Brumbaugh, Graves, Donohue & Raymond ABSTRACT: This disclosureis concerned with dyeing compositions containing certainN-alkyl-ll-carbamylalkyl-isopicramic acid compounds and to methods ofdyeing keratinous fibers with these compositions.

where N is an alkylene group having up to 3 carbon atoms;

N is an alkyl or hydroxyalkyl group having up to 3 carbon atoms, or thegroup R 'NH l and salts thereof. Preferably the salts are alkali oralkaline-earth metal salts or ammonium or substituted-ammonium salts.

Examples of substituted-ammonium salts are ammonium salts in which oneor more of the hydrogen atoms of the ammonium radical is substituted byan alkyl group having up to six carbon atoms or by a hydroxyalkyl grouphaving up to four carbon atoms or in which two hydrogen atoms of theammonium radical are substituted by a group which forms with thenitrogen atom a heterocyclic ring.

As specific examples of metal salts are mentioned the sodium, potassiumand calcium salts. As specific examples of substituted-ammonium saltsare mentioned the monodiand tri-ethanolamino or isopropanolamine,monodiand tri-methylamine, ethylamine, -isobutylamine and morpholinesalts. Salts derived from other amines or basic nitrogen-containingcompounds may also be employed.

The above dyes of the invention color hair a violet shade (which is rarefor a nitro dye) and can be used, for example, in the formulation ofblonde, brown and grey hair colorants. The dyes of the invention are ofparticular value in the formulation ofmedium and dark brown haircolorants.

The preferred dyes of the invention areN-methyl-N-carbamyl-methyl-isopicramic acid and its alkali metal,alkalineearth metal, ammonium and substituted-ammonium salts.

The invention also provides a composition for dyeing keratinous fibers,especially living hair, comprising a dye of the invention in aqueoussolution. The pH of the solution of the dye may vary over a wide rangebut will usually be in the range pH 2 to 12. It is preferable to applythe dyes to living hair from solutions having a pH of less than 9 sincethe uptake by the hair of the dyes is greater at the lower pH, and atthe same time the hair is left in a better condition. Furthermore,solutions of pH above 9 tend to shorten the life of permanent waves.

The dyes of the invention may be used with other suitable nitro dyes toproduce blonde, brown and grey shades. When the violet dyes of theinvention are used in conjunction with a yellow dye as in, for example,the formulation of a composition for producing brown or blonde shades,the yellow dye is preferably 2-nitro-N-methyl-N-acetyl-p-amino-phenol ora salt thereof or N-methyl-N-acetyl-isopicramic acid or a salt thereof,preferably an alkali metal, alkaline-earth metal, ammonium orsubstituted ammonium salt thereof. Compositions containing the violetdyes of the invention and these yellow dyes preferably have a pH in therange 6.5 to 7.5.

The violet dyes of the invention are also advantageously used withblue-violet to violet dyes being compounds having the general formula HOgN N R is an alkyl group or a hydroxyalkyl group having up to 4 carbonatoms; and

R is a hydroxyalkyl group having up to 4 carbon atoms; or

salts thereof. Again, the preferred salts are the alkali andalkaline-earth metal salts and ammonium and substitutedammonium salts.

Since these yellow dyes and blue-violet to violet dyes have similarchemical structures to the violet dyes of the invention, combinations ofthem possess useful properties. For instance, selectivity on certainhairs is minimized and also the fastness of the color of the dyed fiberis good. The combinations also have good stability on storage of thecomposition.

When formulating dyeing compositions comprising the dyes of theinvention in their salt form, the salt may be added as such or it may beformed in situ by including in the formulation the acid form ofthe dyeand the appropriate base.

The invention further provides a process of dyeing keratinous fibersusing the above-mentioned compositions.

Dyes according to the invention can be prepared as illustrated in thefollowing example 1i EXAMPLE 1 Preparation ofN-methyl-N-carbamylmethyl-isopicramic acid ammonium salt.

A 500ml. three-necked flask equipped with an automatic stirrer andattached to an ice-mantle and condenser was used. 30 g. of acetamidewere added to 300 ml. of water containing 12 ml. of glacial acetic acidand stirred until a clear solution was obtained at 48-50 C. 30 g. of theammonium salt of N- methyl-isopicramic acid were then added. Afterstirring for a short time, 19.2 g. of potassium hydroxide dissolved in45 ml. of water were added dropwise over a period of 10 minutes. Thetemperature was then gradually raised over a period of 20 minutes untilthe mixture refluxed at 101 C. After refluxing for 25 minutes the flaskwas cooled externally until the temperature had dropped to 65 C. Afurther addition of 15 g. of chloroacetamide and 6 ml. of glacial aceticacid was then made. After stirring for a few minutes at 65-70 C., 9.6 g.of potassium hydroxide dissolved in 22 ml. of water were added dropwiseover a period of 5 minutes. The temperature was then gradually increasedover a period of 15 minutes and the mixture refluxed for 25 minutesmore. The mixture was then poured into 1200 ml. of cold water. Theaddition of 22 ml. of concentrated hydrochloric acid was then made tomake the solution acid to Congo Red Paper. The solution was cooled from40 to 32 C. and fine reddish-brown needles of N-methyl-N-carbamylmethyl-isopicramic acid crystallized out. Onfiltration, 30 g. of moist dyestuff cake were obtained.

The ammonium salt of N-methyl-N-carbamylmethyl-isopicramic acid wasproduced as follows. The filter cake of N-methyl-N-carbamlmethyl-isopicramic acid obtained above was mixed to asmooth paste with a solution of 1 volume of ammonia (specific gravity0.88) in 2 volumes of methyl alcohol. The dyestuff paste was then driedat 5060 C. in a vacuum oven at reduced pressure (60-70 cm. Hg.) andground in a mortar. The yield of N-methyl-N-carbamylmethylisopicramicacid ammonium salt was 24.0 g. On recrystallization from boiling waterthe pure dyestuff was obtained in the form of fine brown crystals withan olive lustre having a melting point of l84-l 86 C.

The corresponding alkali metal, alkaline-earth metal andsubstituted-ammonium salts are readily prepared in a similar manner byneutralizing the N-methyl-N-carbamylmethyl-isopicramic acid with, forexamplfso dium or potassium hydroxide, calcium carbonate,di-isobutylamine, mono-, dior triethanolamine or morpholine. Themorpholine salt was obtained, on recrystallization from water, in theform of granular, black-violet, dull crystals which melted, withdecomposition, at l71-173 C. The diethanolamine salt was obtained in theform of brown prisms withan olive lustre melting at 157 C. Themonoethanolamine salt was obtained on gregates which had a melting pointof 152-154 C.

Compounds having a hydroxyalkyl group attached to the amino nitrogenatom can also be prepared in a like manner to that described above butstarting from, for example, a salt of N-(Z-hydroxyethyl)-isopicramicacid instead of N-methylisopicramic acid.

Salts of N, N-di-carbamylmethyl-isopicramic acid may be prepared asdescribed in the above example by starting from the ammonium salt ofisopicramic acid instead of from the salt of N-methyl-isopicramic acid.

Dyes having a N-ethyl or N-propyl group instead of a N- methyl group maybe obtained, as described above by employing as starting material theammonium salt of N-ethylor N- propyl-isopicramic acid instead of theammonium salt of N- methyl-isopicramic acid.

Furthermore, compounds having a N-carbamylethyl or N- carbamylpropylgroup instead of a N-carbamylmethyl group may be obtained by employingchloro-propionamide or chloro-butyramide instead of chloro-acetamide.

The N-rnethyl-N-carbamylmethyl-isopicramic acid obtained as describedabove, on recrystallization from boiling water gave the pure dyestuff inthe form of fine, lustrous, brownish-violet needles ofmelting pointl87-189 C.

The invention is further illustrated by the following examples 2 to 6 ofcompositions for dyeing hair. In these examples the percentages arepercentages by weight.

Percent Example i 2 3 4 5 Ammonium salt of N.N-di(2- 0.35 1.00 1. 20 1.5000 liydroxyetliyl)-ispicramic acid. Ammonium salt of N-methyl-N-earbamylmethyl-isopicramic aeid 0 10 0. 12 0.15 0.1875N-inethyl-N-acetyl-isopicramic acid. 0 40 0. 25 0.30 0. 3750 N -methyl-N-acetyl-2-nitro-paraamino-phenol 0. 50 0.00 0, 7500 Formamide. 5. 00 5.00 5. 00 5. 0000 Lauryl polyet lene g1 l i2 2s0(C2H40)uH]. 5. 00 5.005.00 5. 0000 Perfume 0. 50 0. 50 0. 50 0. 5000 Thickener [Carbopol 934 u2 w/w aqueous dispersion of a carboxylic-substituted vinyl polymerneutralized with potassium hydroxide)] 30.00 30. 00 42. 00 45. 0000Water To 100 The following procedure was adopted in preparing the abovecompositions. The dyestuffs, formamide, lauryl polyethylene glycol andwater and, in the case of example 6 the morpholine, were mixed andheated to 7075 C. A 2 percent w/w aqueous dispersion of Carbopol 934 waspartly neutralized with N potassium hydroxide to a pH of 7.0 to 7.5 andperfume mixed in. The mixture containing the dyestuffs was then stirredslowly into the Carbopol 934 paste and stirring continued until ahomogenous paste was obtained. Where necessary the pH ofthe paste wasadjusted to 6.5 to 7.0 by the addition of percent lactic acid or 10percent monoethanolamine.

The above compositions gave (on heads with 3070 percent white hair)natural shades with acceptable fastness to shampooing, light andperspiration. They also had acceptable fastness properties onpermanently waved hair and were free from scalp staining and had a goodconditioning effect on the hair. Example 2 gave a golden blonde shade;example 3 a light brown shade; example 4 a medium brown shade; example 5a dark brown shade; and example 6 a darker brown shade.

- X; a 551m of salon tests, a pH of 6.5 to 7.0 was found to be theoptimum value for the color uptake and for imparting a good conditioningeffect to the hair. A viscosity of 400 to 800 centipoises gave the bestresults in color uptake and permitted the easiest application.

The compositions can be applied with a sponge or brush or from anapplicator to either dry or previously shampooed and towel-dried hair.

What is claimed is:

1. A composition for the direct dyeing of keratinous fibers containingin aqueous solution an effective amount ofa compound ofthe formulaONTQ-NO:

where R is alkylene having up to 3 carbon atoms; R is a group selectedfrom the class consisting of alkyl and hydroxyalkyl having up to 3carbon atoms and the group R" CL'NH or salts thereof selected from thegroup consisting of the alkali metal, alkaline-earth metal, ammonium,and amine addition salts.

2. A composition as claimed in claim 1 wherein said aqueous solutionalso contains an effective amount of a yellow dyestuff selected from thegroup consisting of Z-nitro-N- methyl-N-acetyl-p-amino phenol,N-methyl-N-acetyl-isopicramic acid and salts thereof selected from thegroup consisting of alkali metal, alkaline-earth metal, ammonium andamine addition salts.

3. A composition as claimed in claim 1 wherein said aqueous solutionalso contains an effective amount ofa blue-violet to violet dyestuffbeing a compound selected from the group consisting of compounds of theformula:

where R is a group selected from the class consisting of alkyl andhydroxyalkyl having up to four carbon atoms; and R is hydroxyalkylhaving up to four carbon atoms; and salts thereof selected from thegroup consisting of alkali metal, alkalineearth metal, ammonium andamine addition salts.

4. A composition as claimed in claim 1 wherein the compound isN-methyl-N-carbamylmethyl-isopicramic acid or a salt thereof selectedfrom the class consisting of sodium, potassium, calcium, ammonium,monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine,diisopropanolamine, triisopropanolamine, monomethylamine, dimethylamine,trimethylamine, monoethylamine, diethylamine, triethylamine,monoisobutylamine, diisobutylamine, triisobutylamine and morpholinesalts.

5. A composition as claimed in claim 1 wherein the compound isN-methyl-N-carbamylmethyl-isopicramic acid.

6. Process for the direct dyeing of keratinous fibers comprisingapplying to the fibers an effective amount of a composition containingin aqueous solution an effective amount of a compound of the formula:

where R is alkylene having up to 3 carbon atoms; R is a group selectedfrom the class consisting of alkyl and hydroxyalkyl having up to threecarbon atoms and the group -R'- CO- or salts thereof selected from thegroup consisting of the alkali metal, alkaline-earth metal, ammonium andamine addition salts.

zgz gg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,617,166 Dated November 2, 1971 I Jerzy Josef Bartoszewicz It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

' I I Column 1, lines 13-20 "N is an alkylene group having up to 3carbon atoms; N is an alkyl or hydroxyalkyl group having up to 3 carbonatoms, or the group R -NH l and salts thereof" should be -R' is analkylene group having up to 3 carbon atoms; R is an alkyl orhydroxyalkyl group having up to 3 carbon atoms, or the group -R -CO.NHand salts thereof.-.

line 52, "lower pH" should be --lower pHs-.

Colman 2, line 21, "example li" should be -example l..

line 29, "of acetamide" should be of chloroacetamide--.

Column 4, line 12, "group R- CL-NH should be group RCO'NH lines 72 and73, "-12 -coshould be R1-CO'NH2 Signed and Scaled this Nineteenth Day ofApril 1977 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresring Officer ('ummrlssr'nneruflarenrs and 'Tradcmurkx

2. A composition as claimed in claim 1 wherein said aqueous solutionalso contains an effective amount of a yellow dyestuff selected from thegroup consisting of 2-nitro-N-methyl-N-acetyl-p-amino phenol,N-methyl-N-acetyl-isopicramic acid and salts thereof selected from thegroup consisting of alkali metal, alkaline-earth metal, ammonium andamine addition salts.
 3. A composition as claimed in claim 1 whereinsaid aqueous solution also contains an effective amount of a blue-violetto violet dyestuff being a compound selected from the group consistingof compounds of the formula:
 4. A composition as claimed in claim 1wherein the compound is N-methyl-N-carbamylmethyl-isopicramic acid or asalt thereof selected from the class consisting of sodium, potassium,calcium, ammonium, monoethanolamine, diethanolamine, triethanolamine,monoisopropanolamine, diisopropanolamine, triisopropanolamine,monomethylamine, dimethylamine, trimethylamine, monoethylamine,diethylamine, triethylamine, monoisobutylamine, diisobutylamine,triisobutylamine and morpholine salts.
 5. A composition as claimed inclaim 1 wherein the compound is N-methyl-N-carbamylmethyl-isopicramicacid.
 6. Process for the direct dyeing of keratinous fibers comprisingapplying to the fibers an effective amount of a composition containingin aqueous solution an effective amount of a compound of the formula: